The coupling reaction of styrene with vinylsilanes catalyzed by ruthenium complexes was investigated. RuHCl(CO)(PPh 3 ) 3 ( I ) and RuCl(SiR 3 )(CO)(PPh 3 ) 2 (where R 3 = Me 3 ( II ), Me 2 Ph ( III ), (EtO) 3 ( IV )) were found to be efficient and selective catalysts for the formation of E -1-phenyl-2-silylethene and evolution of ethene. Stoichiometric reactions of styrene with the Ru−Si bonds of II − IV in argon and silylstyrene with the Ru−H bond in air ( I* ) as well as a MS study of the product of the deuterated styrene with vinylsilanes are convincing evidence for the mechanism of the process involving the migratory insertion of styrene into the Ru−Si bond (and vinylsilane into Ru−H bond) followed by β-H (and β-Si) elimination to give phenylsilylethene (and ethene). Kinetic tests (TOF) indicate a prior dissociation of the PPh 3 molecule (or by its oxygenation) from I to yield pentacoordinated RuHCl(CO)(PPh 3 ) 2 which is almost as active as II .
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Marciniec et al. (1997) studied this question.